Sulphocarboxylic esters



Patented Sept. 9, 1941 4 No Drawing. Original application June 24, 1939, Serial No. 280,911. Divided and this application September 3, 1940, Serial No. 355,184

6 Claims. (Cl. 260-400) My invention relates to a new class of chemical substances, and more in particular to a new class or chemical substances particularly adapted for use as detergents, wetting, penetrating, emulsifying, lathering, flotation and anti-spattering' agents, and for frothing purposes.

In certain classes of industries, there is a need for a certain class of chemical substances usually used in relatively small quantities but capable of use in larger quantities to secure an effect principally the result of a wetting action such as at a water-oil interface. In the textile and dyeing industries, for example, there are many situations where a wetting or detergent actionis imperative as, for example, in laundering, bleaching, mercerizing, dyeing or other op-' erations, and many different chemical substances have been produced calculated to reduce surface tension and promote wetting in theseindustries.

The use of prior art substances has not'beenattended with unqualified success in all instances. a

The principal object of my present invention is the provision ofa new class of chemical substances capable of satisfactory use in connection with the problems hereinabove discussed.

Another object is the provision of a new class of chemical substances which are in general of relatively simple structure and can be cheaply made in commercial quantities.

Another object is the provision of a new class of chemical substances having improved wetting characteristics.

Other objects and features of the invention will be apparent from a consideration oi. the following detailed description.

The substances of my invention are, in general, s'ulpho-carboxylic acid esters of higher molecular weight alcohols, the esters containing an aromatic group. More particularly, most of the compounds are esters of aliphatic polyhydroxy derivatives of lipophile materials containing at least four carbon atoms and preferably from eight to eighteen carbon atoms with aromatic sulphonic carboxylic acids. In general,

the compounds include both aromatic and aliphatic groups. Certain of the substances coinprise aromatic sulpho-carboxylic acid esters of aliphaticpo yhydroiw substances, at least one hydroxy group 01 the aliphatic polyhydroxy sub- I stance being esterified with a carboxylic acid containing at least four carbon atoms and preferably of aliphatic or cycloaliphatic character and containing from eight to eighteen carbonatoms. Illustrative examples of compounds falling within the scope of my-invention are as follows:

onion CHzOH l O CHrG--CHHH HOH So far as the aromatic sulpho-carboxylic esters are concerned which are derivatives of polyhydroxy substances, I may select many difierent types of compounds as lipophile groups which are to be esterified with the polyhydroxy substances, principally compounds having lipophile radicals of relatively high molecular weight, For example, the following materials may be utilized as sources of lipophile groups; straight chain and branched chain, saturated and unsaturated, carboxylic, aliphatic (including cycloaliphatic), fatty, aromatic, hydroaromatic, and araliphatic acids including butyric acid, caprylic acid, heptylic acid, caproic acid, capric acid, pimelic acid, sebacic acid, behenic acid, arachic acid', cerotic acid, erucic acid, melissic acid, stearic acid, oleic acid, ricinoleic acid, ricinelaidic acid, ricinostearolic acid, linoleic acid, linolenic acid, lauric acid, myristic acid, palmitic acid, mixtures of any two or more of the above mentioned acids or other acids, mixed higher fatty acids derived from animal or vegetable sources, for example, lard, coconut oil, rapeseedoil, sesame oil, palm kernel oil, 'palm oil, olive oil, ;j :orn oil, cottonseed oil, sardine oil, tallow, bean oil, peanut oil, castor oil, seal oils, whale oil, shark oil and other fish oils, partially or completely hydrogenated animal and vegetable oils such as those mentioned; oxidized and/or polymerized higher fatty acids or higher fatty acids derived from oxidized and/or polymerized triglyceride oils; hydroxy and alpha-hydroxy higher ,carboxylic, aliphatic and fatty acids such as i-hydroxy stearic acid, dihydroxypalmitic acid, dihydroxystearic acid, dihydroxybehenic acid, alpha-hydroxy capric acid, alpha-hydroxy stearic acid, alphahydroxy palmitic acid, alpha-hydroxy lauric acid, alpha-hydroxy myristic acid, alpha-hydroxy coconut oil mixed fatty acids, alpha-hydroxy Si aK margaric acid, alpha-hydroxy arachidic acid, and the like; fatty and similar acids derived from various waxes such as beeswax, spermaceti, Montan wax, coccerin, and carnauba wax and higher molecular weight carboxylic acids derived, by oxidation and other methods, from parafiln wax, petroleum and similar hydrocarbons; resinic and hydroaromatic acids such as hexahydrobenzoic acid, naphthenic acid and abietic acid; araliphatic and aromatic acids such as phthalic acid, benzoic acid, Twitchell fatty acids, naphthoic acid, pyridine carboxylic acid; hydroxy aromatic acids such as salicyclic acid, hydroxy benzoic and naphthoic acids, and the like and substitution and addition derivatives of the aforementioned acids, in particular, halogen addition and substitution derivatives. It will be understood that mixtures of any two or more of said acids may be employed if desired and it will also be appre-v ciated that said acids may contain substituent groups such as sulphate, sulphonic, nitrile, thiocyanogen, carbonyl, amide,- amine or substituted amine, halogen, ketone and other groups. The acids may be employed as such. or in the form of their anhydrides, esters including mono-, di-, triglycerides and the like, amides and acyl halides.

The polyhydroxy substances which provide the linkage between the lipophile group and the arm matic sulpho-carboxylic acid radical may be selected from a large class and include, among those mentioned, glycerol; glycols such as ethylene glycol, propylene glycol, tri-methylene glycol, butylene glycol and the like; polyglycols such as diethylene glycol; pentaerythritol; quercitol; dihydroxy acetone; triethanolamine; tripropanclamine; polyglycerols such as diglycerol, triglycerbl, tetraglycerol and the like including mixtures thereof; carbohydrates and sugars including mono-, diand polysaccharides such as dextrose, sucrose, xylose, arabinose, galactose, fructose, maltose, mannose, dextrin, starch, and the like;

- the natural and synthetic simple and complex glucosides; sugar alcohols such as arabitol, mannitol, sorbitol and dulcitol; and poly-hydroxycarboxylic acids such as tartaric acid, mucic acid, saccharic acid, gluconic acid, glucuronic acid, gulonic acid, mannonic acid, trihydroxyglutaric acid, glyceric acid, carboxylic oxidation products of polyglycerols, others of similar character, and hydroxyethyl and hydroxypropyl ether derivatives of .the above, as, for example:

wherein R is a radicalselected from the group consisting of alkyl, cyclo-alkyl, aryl, aralkyl, and acyl, and substitution products thereof, X is the residue of the aliphatic polyhydroxy sub stance, and v and w are small whole numbers.

From a study ofthe compounds which I list hereinabove, those skilled in the art will understand that I may use many different expedients acid group are concerned. As stated, however, ester linkages are utilized between these two portions of the compound, and the skilled chemist will understand in general the most approved practices in securing this result. Numerous methods are also available for the introduction of the sulphonic acid group. In the case of aromatic sulphonic acids, of course, standard sultion.

The following examples are illustrative of the preparation of compounds falling within the scope of my invention. It will be understood that said examples are given only by way of illustration and are not tobe considered in any way limitative of the true scope of my invention.

Example A 7.5 grams of commercial monostearin (washed and dried) were heated to 100 degrees C. and 4.0 grams of powdered sulpho-benzoic acid anhydride were added the mixture being stirred fora period of -to minutes at a temperature of about 90 degrees C. To the resulting reaction mixture, 100 cc. of isopropyl alcohol were added and the mass was neutralized with 55 cc. of alcoholic KOH (0.472 N) at a temperature of between 40 degrees C. and 50 degrees C. A precipitate formed and the clear alcoholic solution which contained the unreacted fatty matter was de canted. The resulting product consisted of a.

compound having the following structural for-' mula:

The product was an ivory colored solid which could be powdered. It dissolved to form a clear solution in hot water and foamed excellently therein. It possessed good surface tension reducing properties and also functioned effective ly in proportions of the order of 0.5% to reduce the spattering of margarine.

Example B -5.8 grams of the monolauric acid ester of diethylene glycol were heated to 90 degrees C. and

4.0 grams of powdered sulpho-benzoic acid anhydride were added thereto. The temperature dropped to 80 degrees C. but, on continued stirfor forming the compounds in so far as the domi-' nant lipophile group and the aromatic sulphonic ring, it again rose to 90 degrees C. After 5minutes the reaction mixture was heated to 100 degrees C. for 2 to 3 minutes and was then allowed to cool to 40 degrees C.-50 degrees C. 100 cc.

of isopropyl alcohol were then added to the re-. action mass which was then neutralized with 56 cc. of alcoholic KOH (0.472 N). 100 cc. of ether were then added to the alcoholic solution in order to precipitate the desired compound which was then filtered off and dried. -It'comprises a compound having the following formula;

CH;(CH C0-CH,

The product was a white powder, dissolved in water and foamed readily. It functioned to reduce the spattering of margarine and also efiectively reduced the surface tension of water.

Example 0 6.5 grams ofthe monostearic acid ester of ethylene glycol were heated to 100 degrees C. and 4.0 grams of powdered sulpho-benzoic acid anhydride were added, the mixture being stirred for a period of about 10 minutes, the mass becoming a homogeneous syrup. 'It was dissolved in '75 cc. of iso-propyl alcohol and then there was added thereto suflicient alcoholic potassium hydroxide to neutralize the product 'to phenol-- phthalein. A precipitate-formed and the clear alcoholic solution which contained the unreacted matter was decanted. The resulting product contained a. substantial proportion of a compound having the following structural formula The product was soluble in warm water and had foaming and surface tension reducing properties.

Example D 11.6 grams of coconut oil mixed fatty acid monoesters of diethylene glycol and 9.2 grams of sulpho-phthalic anhydride were heated to degrees C. with stirring, after which the temperature spontaneously rose to about degrees C., at which temperature the mass was kept for about 5 minutes. 0n cooling, it became a brown. viscous liquid which dissolved in water and;

showed good foaming properties. To the resulting product 100 cc. of isopropyl alcohol were added and then, in order to neutralize the same to phenolphthalein, cc. of 0.5 N alcoholic potassium hydroxide'were added. The precipitate which formed was filtered from the solution and dried. On being crushed, it was an ivory colored powder which had good surface tension in most cases.

reducing properties. It contained a substantial proportion of a compound having the formula:

(3H2 HQ 640% t COOK Example E 12.8 grams of the mono stearic acid ester of ethylene glycol and 9.2 grams of sulpho-phthalic anyhdride were heated to 85 degrees C. after which the temperature spontaneously rose to about 100 degrees C., the mass being retained which formed was filtered off and dried. It wasa cream colored product, dissolved in warm water, exhibited foaming properties, and contained a substantialproportion of a compound having the following formula:

14 grams of monostearin and 10.0 grams of sulpho-phthalic anhydride were stirred and heated to 110 degrees C. for about 5 minutes. The mass was then cooled to 70 degrees C. and 100 cc. of isopropyl alcohol were added thereto followed by the addition of 150 cc. of 0.5 N alcoholic potassium hydroxide. The mass was cooled to about 40 degrees C. and the alcohol decanted off. To the remaining precipitate, 200 cc. of isopropyl alcohol were added and the mass boiled and then filtered on the Buchner filter. To the precipitate there were added 100 cc. of ether and the mass was filtered again. The final product was a cream colored. solid which dissolved in warm water and exhibited foaming properties. It contained a substantial proportion of a compound having the formula:

Those of my substances which are freely soluble in water may be recovered from their solutions and from'their water solutions in the customary manner by concentrating and crystallizlng. As stated hereinabove, as the mass of the lipophile radical increases, solubility decreases and affinity for water is manifested by the dispersibility in water. From these disper- .sions, my substances may be readily recovered by salting out with suitable soluble electrolytes.

Common salt is very satisfactory for this purpose When salted out of an aqueous dispersion at temperatures ranging from 60 to 95 degrees C., the substances are obtained in the form. of a paste with a water content ranging from approximately 25 to 75%. The more hydrophilic the substance, the greater the water content, and, of course, the salt is present in the water of the paste in approximately the same concentration in which it existed in the dispersion from which the paste was salted out. As I have indicated hereinabove, the lipophile or oleophile. group may be of widely varied character and maybe selected from an extensive class of available materials. The lipophile groups are of generally fatty or oleaginous character or are characterized by an affinity for oils and fats and comprise, for example, alkyl, aralkyl, aryl, ether, amide, ester and like groups containing preferably at least eight carbon atoms. These lipophile groups, which, ingeneral, possess predominantly hydrocarbon characteristics, are most frequently derived from triglyceride oils and fats, higher fatty acids, waxes, mineral oils and other hydrocarbons and the like. As. indicated, such lipophile groups may contain nitrogen, oxygen, sulphur or phosphorus as exemplified, for example, by the higher carboxylic and fatty acid amides of alcohol amines such as caproic, lauric, myristic and stearic acid amides of monethan'olamine, diethanolamine, monopropanolamine, and the like; the caproic, lauric, stearic, oleic and similar monoesters of the glycols such as ethylene glycol and diethylene glycol; the caproic, lauric, myristic, palmitic, stearic and similar fatty acid mono-esters of thiodiglycol, thiodiglycerol, and the like. In all cases, such lipophile materials may be reacted to produce therewith esters of aromatic sulpho-carboxylic acids which fall within the broad scope of my invention.

Many of the compounds of my invention may be represented by the following general formula wherein R is the residue of a polyhydroxy substance in which the hydrogen of at least one 11:- droxyl group is substituted by an alkyl or acyl group containing at least four carbon atoms and preferably between eight and eighteen carbon atoms, X is the carbon-hydrogen residue of the aromatic sulpho-carboxylic acid, Y is a cation, and w is a small whole number, at least one.

In so far as the aromatic sulpho-carboxylic acid group of my compounds is concerned, I may employ a sulpho-benzoate, sulpho-phthallate, sulpho-salicylate, sulpho-naphthenate, anthraquinone-, anthracene-, and phenanthrene-sulphocarboxylic acids, or other similar groups containing an unesterified sulphonic acid radical. The aromatic sulpho-carboxylic acid may contain one or more sulphonic groups and one or more carboxylic groups. In other words, the aromatic sulpho-carboxylic acids may be mono-, dior poly-sulpho in character and they may be mono-, di-, or poly-carboxylic. In many cases, the sulpho-aromatic acid radical may contain substituent groups such as N02, CN, N=CO, halogen, OH, NHz, COOH, alkyl, aralkyl and the like.

The chemical compounds are preferably used in the form of their salts in which case the acid derivatives may be neutralized, in whole or in part, with suitable anti-acid materials. In this connection, considerable latitude and modification may be exercised. In general, inorganic as well as organic anti-acid agents may be employed.

Examples of such agents which may be used satis factorily are bicarbonates of the alkali metals, potassium hydroxide, potassium carbonate, me-

' tallic sodium, sodium hydroxide, sodium oxide, sodium carbonate, ammonium hydroxide, am-

line, alkylol polyamines such, as alkylol deriva-' tives of ethylene 'diamine, mono-methyl monoethanolamine, diethyl monoethanolamine, 1- amino-2, 3-propanediol, 1,2-di-amino-propanol; alkylamines such as ethylamine, propylamine, laurylamine, cetylamine, butylamine, hexylamine, cyclohexylamine, aniline,'toluidines, dimethylamine, diethylamine, N-methyl-N-ethyl amine, triethylamine, trimethylamine, ethylene diamine, diethylene triamine, triethylene tetraamine, betaine, mono-methyl ethylene diamine, monoethyl diethylene tetra-amine, monoallyl amine, hydrazine and substituted hydrazine, aromatic and heterocyclic bases and cyclic nitrogenous substances such as benzylamine, cyclohexylethyl aniline, morpholine, pyridine, dimethylaniline, N-methyl-N-benzyl amine, N -ethyl-N- naphthyl amine, quinoline, quinaldine, piperidine,

alkyl pyridines such as methylpyridine, pyrrolidlnes, nicotine, and homologues and derivatives or substitution products thereof, and, in general, primary, secondary and tertiary amines substituted or not with other radicals, such as hydroxy, alkyl, aryl, cyclo-alkyl groups and the like; quaternary ammonium bases or hydroxides such as tetra-methyl ammonium hydroxide, tetraethyl ammonium hydroxide, quaternary ammomum bases with dissimilar alkyl radicals such as methyl-triethyl ammonium hydroxide, propyl trimethyl ammonium hydroxide; mixtures of any two or more of said bases as, for example, in the case of commercial triethanolamine which consuitable salts of organic or'inorganic character orwith other interface modifying agents. In the dyeing of textiles many of them may be employed as assistants in order to bring about even level shades. Many of them also, may be used in the leather industry as wetting agents in soaking, dyeing, tanning and the softening andother treating baths for hides and skins. Their utility as emulsifying agents enables them to be employed for the preparation of emulsions which may be used for insecticidal, fungicidal and for similar agriculture purposes. They have utility in the preparation of hair washes and hair shampoos, dentifrices of liquid, cream and powder type, cosmetic creams such as cold creams, vanishing creams, tissuecreams, shavingcreams of the brushless and lath'ering typeand similar cosmetic preparations. Another use to which .many

of the agents of my invention may be placed is for the treatment of paper ,or'pap'er pulp or the like. Their capillary or interfacial tensionretains minor proportions of monoand di-ethanolamine. It will be understood that these substituted ammonium compounds or organic nitrogenous bases may be utilized in pure, impure, or commercial form.

The compounds of my invention have utility in various arts in which interface modifying agents are employed. Many of them are resistant to precipitation by calcium and magnesium salts.

and are compatible with acid and alkali media. They may be utilized in washing and laundering and in the textile and related industries wherein they function for wetting, lathering, detergent,

emulsifying, penetrating. softening, finishing,

' dispersing, frothing and foaming purposes. The

the artificially produced fibres, (and fabrics) such as rayon, cellulose acetates, cellulose ethers and alums, perborates such as sodium perborate, and a ducing properties enable them to be employed in the fruit and vegetable industry in order to effect the removal from fruits and the like of arsenical and similar sprays. They possess utility in the ore dressing industry wherein they function effectively in froth flotation and agglomeration processes. Their interface modifying properties also permit their use in lubricating oils and the like enabling the production of effective boring oils, cutting oils, drilling oils, wire drawing oils, extreme pressure lubricants and the like. Many of them may also be used with effect in the preparation of metal and furniture polishes, shoe polishes, in rubber compositions, for breaking or -demulsifying petroleum emulsions such as those of the water-in-oil type which are encountered in oil-field operations, as well as in paints and the.

like, and for various other purposes which will readily occur to those versed in the art in the light of my disclosure herein.

be packaged and sold insuch form preferably mixed with diluents. They may also be utilized for commercial cleansing, laundering and wash in'g operations with advantage.

It will be understood that the products of the present invention may be employed for their various purposes either alone or together with lesser or greater quantities of inorganic or organic compounds. Thus, for example, many of them may be employed together with salts such as sodium chloride, alkali metal phosphates including pyrophosphates and tetraphosphates, sodium sulphate,

the like. Many of said products may be utilized in alkaline or acid media in the presence of sodium carbonate, sodium bicarbonate, dilute acids such as hydrochloric, sulphurous, acetic and simi-. lar inorganic and organic acids. They may also be employed in the presence of such diverse substances as hydrophilic gums including pectin,

tragacanth, karaya, locust bean, gelatin, arabic and the like, glue, vegetable, animal, fish and mineral oils, solvents such as carbon tetrachlo-.-

ride, monoethyl ether of ethylene glycol, monobutyl ether of ethylene glycol, monoethyl and similar artificial silk fabrics and silk andwool substitutes. It will be understood, of course, that the agents may be used in aqueous and other media either alone or in combinationwith other monobutyl ethers of diethylene glycol, cyclo-' hexanol, and the like. They may be used together with wetting, emulsifying, frothing, foaming, penetrating and detergent agents such as the higher molecular weight alkyl sulphates, phosphates, pyrophosphates and tetraphosphates as.

for example, lauryl sodium sulphate, myristyl sodium pyrophosphate, cetyl sodium tetraphos! phate, octyl sodium sulphate, oleyl sodium sulphate, and the like; higher molecular weight sulphonic acid derivatives such as cetyl sodium sulphonate and lauryl sodium sulphonate; sulphocarboxylic acid esters ofhigher molecular weight alcohols such as lauryl sodium sulphoacetate, dioctyl sodium sulpho-succinate, dilauryl potassium sulpho-glutarate, lauryl monoethanolamine sulpho-acetate, and the like; sulphuric and sulphonic derivatives of condensation products of alkylolamines and higher fatty acids; reaction products of phosphoric, pyrophosphoric, meta-phosphoric, tetraphosphoric, and polyphosphoric acids with higher molecular weight alcohols; Turkey-red oils; compounds of the type of isopropyl naphthalene sodium sulphonate, and other classes of wetting agents.

It will be understood that the compounds need not be utilized in the pure state. Indeed, in most 1nstances it willbe found to be more convenient and commercially desirable to employ them in the form of their reaction mixtures with or without the addition of diluents. It will also be understood that mixtures of any one or more of the reacting constituents may be employed in producing the products hereof and this is particularly the case where commercial supplies of the chemicals are utilized.

It will be understood that the term "lipophile group, as employed herein, is intended to cover any radical containing at least four carbon atoms and having an aflinity for oleaginous material such as oils, fats, hydrocarbons and the like and may comprise radicals such as hydrocarbon radicals, acyl or alkyl groups derived from aliphatic or fatty acids or their corresponding alcohols, and the like.

Unless otherwise indicated, the term higher," wherever employed in the claims, will be understood to mean at least eight carbon-atoms and, concomitantly, the term .lower will mean less than eight carbon atoms.

Whenever the term aromatic sulpho-carboxylic ester or the like expression is employed in the claims, it will be understood to cover the compounds irrespective of whether the hydrogen of the sulphonic acid is present as such or replaced by another cation.

My present application is a division of my prior application Serial No. 280,911, filed June 24, 1939.

What I claim as new and desire to protect by Letters Patent of the United States is: 1. A lower molecular weight aliphatic sulphomonocarboxylic acid ester of an aliphatic polyhydroxy substance containing a higher molecular weight radical, said ester containing anaromatic carboxylic acid ester group.

2. An ester of an aliphatic polyhydroxy substance containing a higher molecular weight radical with an aliphatic sulphocarboxylic acid, said ester containing an aromatic carboxylic acid ester group.

3. An ester of an aliphatic polyhydroxy substance containing a higher molecular weight.radi- .cal having from eight to eighteen carbon atoms with an aliphatic sulphocarboxylic acid having less than eight carbon atoms, said ester containing an aromatic carboxylic acid ester group.

4. An ester of an aliphatic polyhydroxy substance containing a higher molecular weight aliphatic radical with a lower molecular weight aliphatic sulphocarboxylic acid, said ester containing an aromatic carboxylic acid ester group. I

5. An ester of a lower molecular weight aliphatic sulpho-carboxylic acid with a derivative of an aliphatic polyhydroxy substance, said latter derivative comprising an aliphatic polyhydroxy substance the hydrogen of at least one hydroxy group of which is replaced by an organic radical containing at least four carbon atoms, said ester containing an aromatic carboxylic acid ester group.

6. A carboxylic ester of sulpho-acetic acid, the sulphonic group of which is unesterified, wherein the radical esterified with the sulpho-acetic acid is an aliphatic polyhydric alcohol radical the hy- 4 drogen of one hydroxy group of which is replaced by a high molecular weight straight chain aliphatic radical, said ester containing an aromatic carboxylic acid ester group.

BENJAMIN R. HARRIS. 

